Acid dyestuff of the anthraquinone series and process of preparing it



Patented Apr. 23, 1935 UNITED STATES PATENT otarce ACID DYESTUFF OF THE ANTHRAQUINONE SERIES AND PROCESS OF PREPARING IT Georg Kriinzlein and Ernst Diefenbach, Frankfort-on-the-Main-Hochst, Germany, assignors ,to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application 0ctober, 2,0, 1933,

Serial No. 694,518. In Germany February 6,

The present invention relates to new acid dyestulfs of the anthraquinone series and a process of preparing them, moreparticularly it relates to blue acid dyestuffs of the general formula:

halogen-anthraquinone-2-sulfonic acid of the formula:

0 NH; II

H O halogen or a salt thereof, with a compound of the formula: I

H2NR-CH2-R1COOH wherein R and R1 represent radicals of the benzene series and the COOH-group in the radical R1 occupies the ortho-position to the Gila-group, or :a salt thereof, by heating the components in the presence of an acid binding agent and asmall quantity of a copper compound.

The new compounds may be used as dyestuffs or .as starting materials for the manufacture of votherdyestuffs.

The same blue acid dyestuffs are obtainable by condensing a Bz'-aminodiphenylmethane-Z-carboxylic acid with a I-amino-ZA-dihalogenanthraquinone and substituting in the l-amino- 2 halogen 4 arylidoanthraquinones thus obtained the sulfonic acid group 'for the halogen atom standing in 2-position of the anthraquinone compound, advantageously by treatment with alkali metal sulfites.

We have furthermore found that the blue acid dyestuffs, obtainable as above described, may be converted into new dyestuffs having entirely different properties, :by treating themwith concentrated sulfuric xacid or a similar agent suchas chlorosulfonic acid. The conversion even occurs under very :mild conditions of reaction, espedaily at low temperatures. The blue dyestuffs .4 Claims. (01. 260-) used as starting materials chiefly yield brown to gray to green dyestufis. The constitution of the new products has not yetibeen definitely ascertained, but most probably ring closure, occurs by the dehydrating action of the sulfuric acid.

This'applica'tion is a continuation-in-part applicationto our copending application Serial No. 512,490 filed January 30, 1931 The following examples serve to illustrate the invention, but they are not intended to limit it 'thereto the parts being by weight:

(1) 40 parts of sodium l-aminol-bromo-anthraquinone-Z-sulfonate are dissolved in 350 partsof water. sodium salt of 3-amino-diphenylmethane-Z-carboxylic acid, 20 parts of sodium bicarbonate and 1.6 parts of cuprous chloride, the mixture is heated; while stirring, at 60 C; to C. until the formation of the dyestuff is finished. The dyestuff, thus formed, which corresponds With the following formula:

SOONB CO'O'Na is precipitated by addition of hydrochloric acid and purified by dissolving it in dilute sodium carbonate solution and re-precipitating it. 10 parts of the blue crystalline dyestuff powder, thus obtained, are introduced, while stirring, into parts of chlorosulfonic acid, the temperature not being allowed to rise above -|-20 C. Thereaction is finished when a test portion taken from the reaction mixture dissolvesin'concentrated sulf-uric acid to a blue solution. After the melt has been introduced into ice water, the dyestuff which has been precipitated, is filtered by suction, Washed and dried. It forms adark crystalline powder which dissolves in water'to a greyish-blue solution .and dyes wool and silk beautiful bluishgrey tints of very good fastness.

(2) 32 parts of 3'-amino-4-ethoXy-diphenylmethane-Z-carboxylic acid are dissolved in :400 parts of'water' and 7 parts of sodium carbonate'. After addition of 40 parts of sodium Lamina-4- bromoanthraquinone-2-sulfonate, 20 parts of sodium bicarbonate and 2 parts of cuprous chloride, the mixture is heated, while stirring, at 60 C. to 70 C. until the formation of the dyestufi is finished. The condensation product is purified inthe usual manner by precipitating it by After addition of 27 5 parts of and silk greenish-blue tints. The dyestuff has the following constitution:

O NH: soloNa cooNa I I NH 0,11 0 1 parts of the product, thus obtained, are gradually introduced while stirring, into 100 parts of chlorosulfonic acid which has been cooled to +5 C. After stirring for one hour, during which time the temperature is not allowed to rise above C., the melt is decomposed by mixing it with ice and the dyestuff, thus precipitated, is filtered by suction, washed and dried. There is obtained a dark crystalline powder which dyes wool and silk green tints of very good fastness to washing and to fulling.

(3) parts of sodium salt of 2-amino-4'- methyldiphenylmethane-Z-carboxylic acid are dissolved in 500 parts of water. After addition of 53 parts of sodium l-amino-4-bromo-anthraquinone-2-sulfonate, 25 parts of sodium bicarbonate and 2,5 parts of cuprous chloride, the mixture is heated, while stirring, at C. to C. until the formation of the dyestuff is finished. The reaction product is then isolated and purified in the usual manner and there is obtained a blue dyestuff powder which dyes the animal fiber clear blue tints. The dyestuff has the following constitution:

O NHi A SOEONQ H l 0 NH COONa 00132-0 CH3 5 parts of the product are introduced at room temperature into 50 parts of concentrated sulfuric acid, while stirring, and the temperature is maintained at +25 C. to 30 C. for three hours. The mixture is then poured into ice water, the dyestuff which has been precipitated in the form of brown flakes, is filtered by suction, washed and dried. The red-brown powder, thus obtained, dissolves in water to a reddish-brown solution and dyes wool and silk brown tints of good fastness.

We claim:

1. The acid dyestuffs, substantially identical with those which are obtainable by causing a compound of the formula:

wherein Z stands for OH or C1, to act upon a compound of the following general formula:

SOaONa wherein the nucleus R may contain a -OC2H5 or a CH3 group as substituent, and the bond from the CH2 group to R is either in ortho or meta position to the NH group under mild conditions of reaction, particularly with regard to the reaction temperature.

2. The acid dyestuffs substantially identical with those which are obtainableby causing chlorosulfonic acid to act at a temperature not exceeding about +25 C. upon a compound of the following general formula:

0 NH; I

COONa wherein X represents hydrogen or a -OC2H5 group.

3. The acid dyestufi, substantially identical with that which is obtainable by causing chloe rosulfonic acid to act at a temperature not exceeding about +20 C. upon a compound of the formula:

O NH:

SOzONa li H COONo.

COONa z so CH2 I forming a dark crystalline powder and dyeing wool and silk green tints of very good. fastness to washing and to fulling.

- GEORG KRANZLEIN.

-ERNSTv DIEFENBACH. 

